JPH07216203A - Decomposable foam and its preparation - Google Patents

Abstract

PURPOSE: To provide a soln. which is prepd. by dissolving lignocellulose and/or its deriv. in a low-mol.-wt. aliph. polyester polyol and which, when foamed and cured, economically gives a novel foam excellent in bio-/photodegradability.

CONSTITUTION: The objective soln. is prepd. by dissolving (A) lignocellulose and/or its deriv. in (B) a low-mol.-wt. aliph. polyester polyol (pref. having a mol.wt. of 300-2,000 and being bio-/photodegradable). The soln. is prepd. usually by stirring 100 pts.wt. component A in 10-1,000 pts.wt. component B under heating (pref. at 200-300°C) for 0.5-5 hr. Component B is obtd. e.g. by the polycondensation of an aliph. dicarboxylic acid (e.g. adipic acid) and a diol (e.g. ethylene glycol).

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decomposable foam and a method for producing the same.

More particularly, the present invention relates to a lignocellulosic melt obtained by dissolving and reacting a lignocellulose and / or a derivative thereof with a low molecular weight biodegradable aliphatic polyester polyol, a method for producing the same, and a lignocellulose melt. The present invention relates to a foam having excellent biodegradability obtained by foaming and curing the same with a foaming agent and a curing agent, and a method for producing the same. Further, a foam having excellent biodegradability and photodegradability (hereinafter referred to as “bio / photodegradability”) obtained by adding a photodegradation accelerator to the above-mentioned dissolved material and foam-curing by the same method, and The present invention relates to a manufacturing method thereof.

Further, it is obtained by foaming and curing a lignocellulose-based solution obtained by dissolving and reacting lignocellulose and / or its derivative in a low molecular weight raw / photodegradable aliphatic polyester polyol with a usual foaming agent and curing agent. The present invention relates to a foam excellent in both biodegradability and photodegradability and a method for producing the foam.

[0004]

2. Description of the Related Art At present, waste plastics are the main cause of environmental pollution, and their disposal is becoming a serious problem in developed countries and South Korea. Traditionally, plastic waste has been disposed of by landfill, incineration, recycling methods, etc. But,
Landfill disposal is currently reaching its limit. The incineration process wastes unnecessary energy and adversely affects global warming due to the generation of carbon dioxide gas, and often causes damage to the incinerator, which poses an economic problem. The recycling method has been recognized as a very good method, and a lot of research is currently in progress, and some of it has been implemented, but there are problems in terms of collection, quality control, standards, etc. The reality is that it has undergone enormous difficulties.

In particular, styropol (expandable polystyrene), which is widely used as a cushioning material for single-use packaging, has a very large volume, making it difficult to secure landfill. Regarding the incineration and recycling methods, the degree of environmental pollution is large, and many countries are currently preparing measures such as adding legal regulations.

On the other hand, the above-mentioned problems are caused by imparting biodegradability or photodegradability to the buffer material, and after a certain period of time after use, the buffer material is decomposed by natural microorganisms or sunlight and automatically circulated to the natural system. Efforts to solve the problem are active. As an example, a biodegradable foam (trade name: NOVON) made from starch and a water-soluble polymer has been developed by NOVON PRODUCT in the United States. This product has high biodegradability because it uses a high content of starch, but it has high hygroscopicity, mechanical properties such as impact resistance are somewhat poor, it is very expensive, and it is widely used in practice. Hasn't arrived yet. In addition, Showa High Polymer Co., Ltd. of Japan succeeded in developing a synthetic biodegradable aliphatic polyester (trade name: BIONOLLE) foam, and is rushing for mass production, but it is very economical Difficulties are expected.

On the other hand, lignocellulose is mixed with cellulose, hemicellulose, lignin and the like.
Wood flour, rice husk, rice straw, etc., which are mentioned as examples of lignocellulose, have the property of being easily decomposed by microorganisms in the natural world and have no crystallinity even though they have a crystal structure that contributes to mechanical properties. There are many technical problems. For this reason, most of it is currently discarded, but it is an enormous amount of waste resources, and there is an urgent need for a measure to utilize this waste resource at a high level.

[0008]

The present inventor effectively utilizes so-called lignocellulose such as waste wood powder and rice husk that can be obtained at a very low price, and not only has excellent decomposition characteristics but also has good economical efficiency. As a result of earnest researches to obtain a decomposable foam that can be replaced with a single-use cushioning material such as styropol, the present invention has been achieved.

It is an object of the present invention to provide a lignocellulosic melt used in the production of degradable foams and a process for their production. Another object of the present invention is to provide a novel foam excellent in both biodegradability and photodegradability and a method for producing the same.

[0010]

The decomposable foam and the method for producing the same according to the present invention for achieving the above object are obtained by converting lignocellulose and / or a derivative thereof into a low molecular weight biodegradable aliphatic polyester polyol. The present invention relates to a lignocellulosic solution that has undergone a dissolution reaction and a method for producing the same, and a foam having excellent biodegradability obtained by foaming and curing a lignocellulosic solution with an ordinary foaming agent and a curing agent, and a method for producing the same. . The present invention also relates to a foam having excellent raw / photodegradability, which is obtained by adding a photodegradation accelerator to the above-mentioned melt and foam-curing the same method, and a method for producing the same.

Further, a lignocellulosic solution obtained by dissolving and reacting lignocellulose and / or a derivative thereof in a low-molecular weight raw / photodegradable aliphatic polyester polyol, a method for producing the same, and ordinary foaming of the lignocellulosic solution. Raw material obtained by foaming and curing a curing agent and a curing agent
The present invention relates to a foam having excellent photodegradability and a method for producing the foam. The present invention will be described in detail below.

In the present invention, the lignocellulose derivative means a substance produced by a chemical modification reaction such as partial etherification or esterification of a reactive group contained in lignocellulose, for example, a hydroxyl group. The manufacturing method is disclosed in Japanese Laid-Open Patent Publications Sho 56-135552 and Sho 57-
2360, Sho 57-103804, Sho 61-13872
2, Sho 61-171744, Sho 61-215675, Sho 61-215679, Sho 63-63769 and the like.

The method for producing the above-mentioned lignocellulose derivative will be briefly described. For example, a lignocellulose derivative using wood flour is prepared by finely pulverizing wood flour in the presence of a solvent such as water or a swelling agent. After the etherification or esterification reaction of the hydroxyl group contained in the lignocellulose at room temperature or under heating, it is filtered, washed with water or alcohol, and dried.

For the esterification, various acids such as acid halides, dibasic acid anhydrides and aliphatic acids are used. Also,
Etherification includes halides such as methyl chloride, ethyl chloride, aryl chloride, benzyl chloride and epichlorohydrin, α-halogen acids such as monochloroacetic acid, dialkyl acetic acid such as dimethyl acetate and diethyl acetate, ethylene oxide, propylene oxide. An epoxy compound such as, a vinyl compound activated with a negative group such as acrylonitrile, an aldehyde such as diazomethane or formaldehyde, or an organometallic compound such as titanium alkylate is used. Further, these reactions are carried out without a catalyst or under a catalyst. In the former case, a catalyst such as sulfuric acid, perchloric acid, pyridine or zinc chloride can be used, and in the latter case, an alkali catalyst such as caustic soda can be used.

Preferable examples of the organic group to be introduced include aliphatic acyl groups such as acetyl group, propionyl group, butyryl group and valeryl group, dibasic acid monoester groups such as carboxypropenoyl group, benzoyl group and other groups. Aromatic acyl group, methyl group, lower alkyl group such as ethyl group, aryl group, carboxymethyl group, hydroxyalkyl group such as hydroxyethyl group, polyoxymethylene group, polyoxyalkylene glycol group such as polyoxyethylene glycol group, Examples thereof include long-chain alkyl groups such as benzyl group, pentyl group and octyl group, cyanoethyl group, methylene ether group and the like. It is also possible to introduce two or more of these organic groups.

Among the various treatment methods, the lignocellulose derivative suitable for the present invention is a methyl group, an ethyl group, a benzyl group, an aryl group, an acetyl group, a hydroxyethyl group in consideration of the price of raw materials and the physical properties of the final product. , A carboxymethyl group, a monoester group derived from maleic acid or phthalic acid, and the like are chemically modified products.

The biodegradable aliphatic polyester polyol in the present invention is obtained by subjecting an aliphatic dicarboxylic acid and a diol to a general polycondensation reaction and / or obtained by ring-opening polymerization of an aliphatic cyclic ester monomer. Is used. The raw / photodegradable aliphatic polyester polyol used in the present invention is obtained by subjecting a dicarboxylic acid composed of an aliphatic dicarboxylic acid and a ketone dicarboxylic acid and an aliphatic diol to an ordinary polycondensation reaction.

As the aliphatic dicarboxylic acid, those having an aliphatic carbon number of 8 or less can be used. Further specific examples thereof include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and their methyl and ethyl derivatives. As the ketone-based dicarboxylic acid or its ester, it is possible to use an aliphatic carbon number containing a ketone group having 8 or less. Specific examples thereof include acetylsuccinic acid, β-acetylglutaric acid, γ-acetylpimelic acid, γ-benzoylpimelic acid, γ-acetylsuberic acid, γ-acetylazelaic acid, and 3-oxoglutaric acid. And these methyl and ethyl derivatives can be used. Also, as the diol, there are still 2 hydroxy groups having 8 or less carbon atoms.
A variety of diols can be used, and specific examples thereof include ethylene glycol, propylene glycol,
1,4-tetramethylene glycol, 1,5-pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, octamethyl glycol, diethylene glycol, triethylene glycol and the like can be used.

As the aliphatic cyclic ester type monomer,
It is desirable if the ring-opening reaction is carried out by a known method,
Specific examples thereof include β-propiolactone, β
-Butyrolactone, α, α'-bischloromethylpropiolactone, α, α'-dimethyl-β-propiolactone, δ-valerolactone, β-ethyl-δ-valerolactone, 3,4,5-trimethoxy- δ-valerolactone, 1,4-dioxan-2-one, glycolide, lactide, 1,4-dithian-2,5-dione, trimethylene carbonate, neopentylene carbonate, ethylene oxalate, propylene oxalate, ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, 4-methyl-7-isopropyl-ε-caprolactone, 3,3,5-trimethyl-ε- Caprolactone,
There are cis-disalicylide, trisalicylide, etc.,
Considering economy, ε-caprolactone, lactide,
Glycolide is the best choice.

In the present invention, the amount of the dicarboxylic acid composed of the fatty dicarboxylic acid and the ketone dicarboxylic acid or the ester thereof at the time of synthesizing the aliphatic polyester polyol is 5 to 5 when viewed as a molar ratio relative to the aliphatic diol.
Excessive addition in the range of 20 mol% is desirable. The reason is to obtain a polyol having a hydroxyl group bonded to the terminal of the polymerized polyester.

The content of the ketone-based dicarboxylic acid and its ester in the total amount of dicarboxylic acid during the synthesis of the raw / photodegradable aliphatic polyester polyol in the present invention is 0.01.
If the amount is less than mol%, the photodecomposition performance is inferior, and if it is more than 5.0 mol%, the economical efficiency is inferior because the ketone dicarboxylic acid is expensive. The content of the ketone-based dicarboxylic acid and its ester is optimally in the range of 0.3 to 2 mol% in view of photodegradability and economical aspects.

The molecular weight of the aliphatic polyester polyol used in the present invention is preferably in the range of 200 to 5,000, and most preferably in the range of 300 to 2,000.
A polymer having a molecular weight of less than 200 is advantageous from the viewpoint of solution reaction with lignocellulose and / or its derivative, but has a high degree of curing with a curing agent, that is, a high degree of crosslinking, and thus has a problem of poor biodegradability. If the molecular weight exceeds 5,000, there is a drawback that the solution reaction is not performed well.

In the present invention, lignocellulose and / or
Alternatively, a solution obtained by dissolving the derivative thereof in an aliphatic polyester polyol is usually about 10 to 1000 parts by weight of the aliphatic polyester polyol with respect to 100 parts by weight of lignocellulose and / or a derivative thereof, and heated to about Obtained by reacting with stirring for 0.5 to 5 hours. When the amount of the aliphatic polyester polyol to be added is less than 10 parts by weight, the solution is not sufficiently solubilized, and there is a problem that the mechanical properties of the foam targeted by the present invention are deteriorated. If the amount exceeds 1,000 parts by weight, the cost of the aliphatic polyester polyol is high, and there is a problem that the economy is poor. In order to solve these problems, it is possible to add an appropriate amount of low-cost polyhydric alcohol having a low molecular weight such as ethylene glycol or propylene glycol, or a polyether polyol such as polyethylene glycol or polypropylene glycol in some cases. Is. In this case, if the amount of addition is too large, there is a drawback that the biodegradability of the foam finally obtained becomes poor, so it is desirable to add in consideration of this.

Generally, the heating condition is preferably 100 to 300 ° C, and optimally 200 to 300 ° C. The higher the temperature, the better the solution state, but if the temperature exceeds 300 ° C., the phenomenon of carbonization of lignocellulose and / or its derivative is generated, which is not preferable. A small amount of acid catalysts such as hydrochloric acid, sulfuric acid, and Lewis acid can be added to further promote the solution reaction, but in this case, the solution state becomes unstable such that the recondensation reaction of lignin occurs if left as it is, It is desirable to neutralize with an alkali or to remove the precipitate as a double salt.

By subjecting the lignocellulosic solution of the lignocellulose and / or its derivative and the biodegradable aliphatic polyester polyol obtained as described above to foam-curing in the presence of a conventional foaming agent and curing agent, The foam object of the present invention is obtained. Examples of the curing agent include methylene diphenyl diisocyanate (M
DI), polyvalent isocyanate compounds such as tolylene diisocyanate (TDI), polyvalent glycidyl compounds, and melamine derivatives can be used. Further, as the foaming agent, it is possible to use a low boiling point solvent such as cyclopentane, hexane, freon, alternative freon, or water. It is most desirable to use water as a foaming agent in consideration of recent environmental pollution such as Freon. In order to improve the physical properties of the foam, it is desirable to use a foam stabilizer, and in particular, a silicone-based foam stabilizer used during the production of ordinary polyurethane foam is most suitable. In addition, a usual amine-based or tin-based catalyst or the like may be used to accelerate the foam curing reaction.

The amounts of the foaming agent, foam stabilizer and catalyst added in the process of producing the foam are 5 to 50 parts by weight per 100 parts by weight of the usual lignocellulosic melt, respectively.
It is desirable to add 0.1 to 2.0 parts by weight and 0.1 to 2.0 parts by weight, and the curing agent is a mixed solution 1 containing the above additives.
It is desirable to add 60 to 150 parts by weight to 00 parts by weight.

The foam obtained by the above method is not only excellent in biodegradability but also economical. Further, since the decomposition property is further improved, a decomposable foam having further photodecomposition property can be obtained. This can be achieved by adding a photodegradation accelerator to a solution of the lignocellulose and / or its derivative and the biodegradable aliphatic polyester polyol and foaming and curing the same with a usual foaming agent and curing agent. it can.

The photodegradation accelerator used in the present invention is US Pat. Nos. 3,797,690, 3,860,538, 4,121,025, 4,461,853 and 3,676. , 401, 2,495,286, 3,083,184, Japanese Published Patent Application No. 48-5415.
3, known compounds such as 50-21079, 50-34340, and the like, for example, condensation products of aldol and α-naphthylamine, metal dialkyl-dithiocarbamates such as acetylacetone, cobalt dimethyl-dithiocarbamate, salicyl. Aldehydes, α-mercaptobenzothiazole, copper acetate, fatty acid metal salts such as zinc stearate, thiodipropionic acid, iron acetylacetonate, metal acetylacetonates such as cobalt acetylacetonate, α-naphthoquinone, anthraquinone and derivatives thereof, Propiophenone, benzophenone and its derivatives, vinyl-ketone copolymer (ECOLYTE
ATLANTIC, product name: ECOLYTE), ethylene-carbon monoxide copolymer (UNION CARBIDE, product name; DXM-439), and the like, and it is desirable to use one or more kinds in combination. The addition amount varies depending on the kind of the photodegradation accelerator, but is usually 0.00 per 100 parts by weight of the dissolved product of lignocellulose and / or its derivative and the aliphatic polyester polyol.
1 to 5 parts by weight is desirable, and 0.01 to 3 parts by weight is optimal. When the addition amount is less than 0.001 part by weight, sufficient photolytic properties cannot be obtained. On the other hand, when the addition amount is more than 10 parts by weight, the photodegradability is excellent, but mechanical properties become poor,
Since the additives are expensive, there is a drawback that economic efficiency deteriorates.

In order to improve the degrading property, lignocellulose and / or a derivative thereof and a biodegradable aliphatic polyester polyol in place of the biodegradable aliphatic polyester polyol are mixed with an aliphatic dicarboxylic acid and a ketone dicarboxylic acid. A dicarboxylic acid composed of an acid or an ester thereof is subjected to a polycondensation reaction with an aliphatic diol, and a lignocellulosic melt is produced by the above-mentioned method to foam and cure a foaming agent and a curing agent. A foam having excellent degradability was produced.

[0030]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples. The physical property evaluation methods in the examples are as follows. Density The density was measured by the method of ASTM D3574 after producing a specimen with a volume of foam larger than 1000 mm ³ . Hardness (25% ILD) Manufacture the size of the specimen to 380 x 380 x 20 mm or more, and make 25% ILD by the method of ASTM D 3574.
(INDENTATION LOAD DEFLECTION VALUE) was measured. Aspergillus niger, which is often found in soil using solid agar medium after cutting biodegradable samples to a certain size, Aspergillus flavus
(ASPERGILLUS FLAVUS), Penicillium funiculosum (P
ENICILLIUM FUNICULOSUM) and PULLULARIA PULLULANS mixed spore suspensions were sprayed, and the degree of mold cover on the sample was recorded as follows to measure the biodegradation characteristics. When not growing (0%): 0 10% or less: 110 ~
At 30%: 2 At 30-60%: 3 At 60-100%: 4 After cutting a photodegradable sample into a certain size, a weather resistance tester (ATAL
Xenon ARC)
After being left to stand, the time until the hardness was 5% or less of the initial hardness was measured.

Examples 1 to 5 (1) Production of a solution of wood flour and polycaprolactone A solution of wood flour, which is one of lignocellulose, and polycaprolactone, which is one of aliphatic polyesters, was produced. 100 parts by weight of wood flour of 20 to 80 mesh size dried at 110 ° C for 10 hours or more and polycaprolactone of various molecular weights (trade name: TONE POLYOL, Union Carbide
400 parts by weight in a pressure-resistant stainless steel polymerization vessel, sealed and heated at 250 ° C. for 2.5 hours with stirring to give about 100
A brown melt having a viscosity of about 0 cp was obtained. (2) Manufacture of foam 100 parts by weight of the melt obtained in (1) above, 10 parts by weight of water as a foaming agent and a silicone type foam stabilizer L-5740M (Uni
on Carbide) (1.5 parts by weight) and mixed well, then 0.3 parts by weight of amine catalyst DABCO33LV (manufactured by Aldrich, USA) and 0.3 parts by weight of tin catalyst Tin Octoate (Tin Octoate). 50 parts by weight of hardener MDI and well mixed, and then mixed well.
Heated to ° C. After 2-3 minutes, foaming and curing were completed to obtain a degradable soft foam. The results of the physical properties are shown in Table 1.

[0032]

[Table 1]

Examples 6 to 10 (1) Production of Methylated Wood Flour Methylated wood flour was produced as one of the derivatives of lignocellulose. First, dried Radiata pine tree (Radiata
pine) Wood flour (20-60 mesh) 50g is put into a 1 liter size reaction flask, and toluene 500g.
Was added. Then add 40 g of caustic soda to the aqueous solution,
The mixture was stirred for 1 hour at room temperature to form micelles. Then 60 ml
Of methyl iodide was added, the vessel was sealed, the temperature was raised to 80 ° C., and the reaction was performed for 3 to 6 hours. At the end of the reaction, stop the stirrer, and the reaction system separates into two layers, so remove the upper layer of toluene diagonally and pour a mixture of acetic acid acid acetone / methanol (volume ratio 3: 7) to stir to neutralize. After washing and removing the supernatant liquid, excess acetone was continuously added and stirred in the same form, washed and filtered twice, dried in a hot air dryer at 60 ° C for 1 day, and finally at 50 ° C. A sample was obtained by vacuum drying. The methylated wood flour obtained was a yellowish yellowish powder solid and had a weight gain of 10%. (2) Production of Melt of Methylated Wood Flour and Polycaprolactone 100 parts by weight of the methylated wood powder obtained in (1) above and 400 parts by weight of polycaprolactone of various molecular weights were placed in a pressure-resistant stainless steel polymerization container and sealed. Then, the mixture was heated and stirred at 230 ° C. for 3 hours to obtain a dark brown viscous melt. (3) Production of foam Using the melt obtained in (2) above, a cross-linking agent, a foaming agent, a foam stabilizer and a catalyst having the same composition as in Examples 1 to 5 are added and mixed well. Upon curing, a degradable soft foam was obtained. The results of the physical properties are shown in Table 2.

[0034]

[Table 2]

Examples 11 to 15 (1) Production of acetylated wood flour Acetylated wood flour was produced as a different example of the lignocellulose derivative. Dried tropical keruing (kerui
ng) To 10 g of wood flour (20 to 60 mesh), 6.0 ml of acetic anhydride and 40.0 ml of acetic acid were added, and the mixture was left overnight at room temperature. Then, an acylating agent obtained by mixing 100.0 ml of acetic anhydride, 60.0 ml of acetic acid, and 0.2 ml of perchloric acid was cooled at around -10 ° C, and wood flour after pretreatment was added. The reaction was performed in a 300 ml round bottom three neck flask. After injecting the mixed acid, the mixture was left at room temperature for 1 hour and reacted at 30 to 45 ° C. for 6 hours while stirring. After the reaction, the product was thoroughly washed with water, filtered through a glass filter, and produced in the same manner as in the above methylated wood flour. The obtained acetylated wood flour had the same hue as that of wood, and the weight increase rate was 60%. (2) Production of polyhexamethylene succinate Polyhexamethylene succinate, which is one of the aliphatic polyesters, was produced. The molar ratio of 1,6-hexanediol and succinic acid was adjusted to about 1.02: 1, with a slight excess of diole, and the catalyst titanium propoxide was adjusted to about 0.5% by weight of the total amount of the monomers. After adding to the three-necked flask, gradually heat with stirring to 2 ° C at 160 ° C.
After reacting for a period of time, the reaction time is adjusted within a range of about 2 to 5 hours while removing water generated by the esterification reaction using an aspirator in a vacuum, and polyhexamethylene succinate of various molecular weights (Table 3) was obtained. (3) Production of a solution of acetylated wood flour and polyhexamethylene succinate A solution of the acetylated wood flour and polyhexamethylene succinate obtained in the above (1) and (2) was produced. .
100 parts by weight of acetylated wood powder and 400 parts by weight of polyhexamethylene succinate having various molecular weights were placed in a pressure-resistant stainless steel polymerization vessel, sealed, and then heated and stirred at 200 ° C. for 2 hours to obtain a brown viscous melt. (4) Production of foam Using the melt obtained in (3) above, a cross-linking agent, a foaming agent, a foam stabilizer and a catalyst having the same composition as in Examples 1 to 5 are added and mixed well. The foam was cured to obtain a degradable soft foam. The physical property results are shown in Table 3.

[0036]

[Table 3]

Examples 16 to 20 (1) Production of Dissolved Product of Wood Flour, Polycaprolactone and Photodegradation Promoter Dissolved product of wood flour and polycaprolactone (molecular weight 425) obtained in the above Example 1 (wood Powder / Polycaprolactone =
Various photodegradation accelerators (100/400 weight ratio) were added in various compositions (see Table 4) to produce raw / photodegradable lysates. The photodegradation promoters used here are iron acetylacetonate, cobalt stearate and salicylaldehyde. (2) Production of Foam Using the melt obtained in (1) above, a crosslinking agent, a foaming agent, a foam stabilizer and a catalyst having the same composition as in Examples 1 to 5 were added and mixed well. The foam was cured to obtain a degradable soft foam. The physical property results are shown in Table 4.

[0038]

[Table 4]

Examples 21 to 25 (1) Production of Raw / Photodegradable Aliphatic Polyester Polyol Production of raw / photodegradable aliphatic polyester polyol is 1
2.49 mol of adipic acid, 0.015 mol of acetylsuccinic acid and 2.63 mol of diethylene glycol were placed in a liter stainless steel reactor and the temperature was raised to 150 ° C. for 1 hour in an autoclave reactor with a distillation tube under a nitrogen atmosphere. After stirring, the titanium propoxide of the catalyst was added to the reaction tank in an amount of about 0.5% by weight based on the total amount of the monomers.
The mixture was gradually heated with stirring and reacted at 170 ° C. for 4 hours to obtain an aliphatic polyester. In addition, various low molecular weight bio / photodegradable aliphatic polyesters (see Table 5) while changing glycol and dicarboxylic acid and ketodicarboxylic acid
Got

[0040]

[Table 5]

(2) Production of Melt of Wood Flour and Raw / Photodegradable Aliphatic Polyester Polyol of Low Molecular Weight Wood flour which is one of the lignocelluloses and raw / photodegradable fat produced in (1) above A lysate with a group polyester polyol was prepared. 2 dried at 110 ℃ for more than 10 hours
100 parts by weight of wood powder having a size of 0 to 80 mesh and 400 parts by weight of the aliphatic polyester produced in the above (1) were placed in a pressure-resistant stainless steel polymerization container and sealed, and then at 250 ° C. for 3 days.
The mixture was heated and stirred for an hour to obtain a brown melt having a viscosity of about 2000 cp. (3) Production of Foamed Product 100 parts by weight of the melt obtained in (2) above, 30 parts by weight of water as a foaming agent, and a silicone-based foam stabilizer L-580 (US U.S.A.
nion Carbide) (1.0 part by weight) and mixed well, then 0.5 parts by weight of amine-based catalyst DABCO33LV (Aldrich, USA) and 0.5 parts by weight of tin-based catalyst dibutyltin dilaurate, and mixed well. When 130 parts by weight of the curing agent MDI was added to the above solution and mixed well,
After 2-3 minutes, foaming and curing were completed and a degradable soft foaming agent was obtained. The physical property results are shown in Table 6.

[0042]

[Table 6]

Examples 26 to 30 (1) Production of Melt of Rice Husk and Raw / Photodegradable Aliphatic Polyester of Low Molecular Weight Rice husk which is one of lignocellulose and raw / photodegradable aliphatic polyester Samples 1 to 1 A lysate with 5 was prepared. 11
100 parts by weight of rice husk having a size of 20 to 80 mesh and dried at 0 ° C. for 10 hours or more, and one of samples 1 to 4
00 parts by weight was placed in a pressure-resistant stainless steel polymerization vessel, sealed, and then heated and stirred at 250 ° C. for 3 hours to obtain a brown melt having a viscosity of about 2000 cp. (2) Production of Foamed Body 100 parts by weight of the melt obtained in (1) above, 30 parts by weight of water as a foaming agent, and a silicone-based foam stabilizer L-580 (US Un
Ion Carbide) (1.0 parts by weight) and mixed well, then 0.5 parts by weight of amine catalyst DABCO33LV (Aldrich, USA) and 0.5 parts by weight of tin catalyst dibutyltin dilaurate were added. When 130 parts by weight of the curing agent MDI is added to the well mixed solution and mixed well,
After 3 minutes, foaming and curing were completed to obtain a degradable soft foam.
The physical property results are shown in Table 7.

[0044]

[Table 7]

Comparative Examples 1 and 2 100 parts by weight of the wood powder used in Example 1 and 400 parts by weight of polycaprolactone having a molecular weight of 150 and 6000 were placed in a pressure-resistant stainless steel polymerization vessel, sealed, and then heated and stirred at 230 ° C. for 3 hours. A dark brown viscous melt was obtained. Using the thus obtained melt, a curing agent, a foaming agent, a foam stabilizer and a catalyst having the same composition as in Examples 1 to 5 were added and mixed well and cured to obtain a decomposable soft foam. It was The physical property results are shown in Table 8.

Comparative Examples 3 to 5 Polyether type polyol (trade name: KONIX PP-2000, GP-30) was used in place of the melt of the lignocellulose and / or its derivative and the aliphatic polyester.
00, FA-703, manufactured by Korea Polyol Co., Ltd.), a curing agent, a foaming agent, a foam stabilizer and a catalyst having the same composition as in Examples 1 to 5 are added, and the mixture is well mixed and foamed to form a raw material usually from Styropol. A polyether-based soft and semi-rigid polyurethane foam, which is known to have some good degradability, was obtained. The physical property results are shown in Table 8.

[0047]

[Table 8]

[0048]

EFFECT OF THE INVENTION The foam obtained according to the present invention is excellent in mechanical properties and is economical because it uses waste resources to be discarded as a raw material. It is a groundbreaking thing that is not decomposed into environmental pollution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Dengyuan, Hanbap, Shinseong-han, 102-905, Incheon-gu, Yuseong-gu, Daejeon, Republic of Korea

Claims (20)

[Claims] 1. A lignocellulosic melt, which is obtained by dissolving lignocellulose and / or a derivative thereof in a low molecular weight aliphatic polyester polyol. 2. The lignocellulosic lysate according to claim 1, wherein the lignocellulose is wood flour, rice husk or rice straw. 3. A lignocellulosic derivative is one in which an organic group is substituted and introduced into a part of a reactive group of lignocellulose, and the organic group is an aliphatic acyl group, a dibasic acid monoester group, or an aromatic group. One or more selected from the group consisting of an acyl group, a lower alkyl group, an aryl group, a carboxymethyl group, a hydroxyalkyl group, a polyoxyalkylene glycol group, a benzyl group, a long chain alkyl group, a cyanoethyl group, and a methylene ether group. The lignocellulosic lysate according to claim 1, wherein the lignocellulosic lysate is present. 4. The lignocellulosic melt according to claim 1, wherein the aliphatic polyester polyol has a molecular weight of 200 to 5,000. 5. The lignocellulosic melt according to claim 1, wherein the aliphatic polyester polyol is a biodegradable aliphatic polyester polyol. 6. The biodegradable aliphatic polyester polyol is a compound produced by polycondensing an aliphatic dicarboxylic acid and a diol and / or a compound produced by ring-opening polymerization of an aliphatic cyclic ester monomer. The lignocellulosic melt according to claim 5, wherein the lignocellulosic melt is present. 7. The lignocellulosic melt according to claim 6, wherein the aliphatic dicarboxylic acid has an aliphatic carbon number of 8 or less. 8. The lignocellulosic melt according to claim 6, wherein the aliphatic diol has 8 or less carbon atoms. 9. The lignocellulosic melt according to claim 5, further comprising a photodegradation accelerator. 10. The photodegradation accelerator is a condensate of aldol and α-naphthylamine, acetylacetone, metal dialkyldithiocarbamate, salicylaldehyde, α-mercaptobenzothiazole, an aliphatic metal salt, thiodipropionic acid, metal acetylacetoacetate. Nate, α-naphthoquinone, anthraquinone and its derivatives, propiophenone, benzophenone and its derivatives, vinyl-ketone copolymers, ethylene-carbon monoxide copolymers and at least one selected from the group consisting of The lignocellulosic lysate according to claim 9, characterized in that 11. The lignocellulosic melt according to claim 1, wherein the aliphatic polyester polyol is a raw / photodegradable aliphatic polyester polyol. 12. The raw / photodegradable aliphatic polyester polyol is produced by polycondensing a dicarboxylic acid composed of an aliphatic dicarboxylic acid and a ketone dicarboxylic acid or an ester thereof with an aliphatic diol. The lignocellulosic lysate according to claim 11, characterized in. 13. The lignocellulosic melt according to claim 12, wherein the aliphatic dicarboxylic acid and the ketone dicarboxylic acid or the ester thereof has an aliphatic carbon number of 8 or less. 14. The lignocellulosic lysate according to claim 13, wherein the ester of dicarboxylic acid is a methyl or ethyl ester derivative of dicarboxylic acid. 15. The lignocellulosic melt according to claim 12, wherein the aliphatic diol has 8 or less carbon atoms. 16. A degradable foam produced by subjecting the lignocellulosic solution according to any one of claims 1 to 15 to foam-curing with a usual foaming agent and a curing agent. . 17. A ligno characterized in that after mixing lignocellulose and / or a derivative thereof with a low molecular weight aliphatic polyester polyol, the mixture is heated with stirring at 100 to 300 ° C. for 0.5 to 5 hours. A method for producing a cellulosic melt. 18. The method for producing a lignocellulosic melt according to claim 17, wherein a biodegradable aliphatic polyester polyol is used as the aliphatic polyester polyol. 19. The lignocellulosic lysate according to claim 18, wherein a photodegradation accelerator is added to a mixture of lignocellulose and / or a derivative thereof and a low molecular weight biodegradable aliphatic polyester polyol. Manufacturing method. 20. The method for producing a lignocellulosic melt according to claim 17, wherein a raw / photodegradable aliphatic polyester polyol is used as the aliphatic polyester polyol.